{"id":{"repo_id":"cape-town","oai_identifier":"oai:open.uct.ac.za:11427/15706"},"canonical_url":"https://search.dev.ndltd.org/etd/cape-town/oai:open.uct.ac.za:11427/15706","repository":{"repo_id":"cape-town","name":"University of Cape Town","base_url":"https://open.uct.ac.za/oai/request"},"display":{"title":"Hemiaminals : a new chemotype for organocatalysis","abstract":"Jorgensen and List introduced enantioselective α-amination of an aldehyde with an azodicarboxylate as the electrophile using L -proline enamine catalysis in 2002. Following borohydride reduction, the α-hydrazino alcohol was obtained in high yield (93-99%) and enantioselectivity (86-97%). Application of the enantioselective α-amination reaction to an acetal as a masked aldehyde was developed in our group recently, and in part I of this thesis results on extending this chemistry to the α-amination of N-protected hemiaminals from N-heterocycles are reported, in which it was found that the reaction only worked with the carbonyl group exo to the ring. In the case of the hemiaminal derived from N-Boc or N-CBz 2-pyrrolidinone an amination with proline catalyst in acetonitrile over 3 days gave α-aminated products in high ee (77-84%). N-N bond hydrogenolysis using Raney Nickel and hydrogen, followed by oxidation to the lactam afforded the N -protected α-amino lactam in high enantioselectivity (78% and 8 6 %). In part II the development of a mild reduction of the N-N bond of the α-hydrazino amination products of straight-chain aldehydes is reported. The corresponding oxazolidinone- hydrazides are reduced to their oxazolidinones via a modified E1cB elimination using ethyl bromomalonate and potassium carbonate in acetonitrile. The reactions gave high yields (76-96%) and ees (83-95%) with a good chemoselectivity profile.","abstract_html":"Jorgensen and List introduced enantioselective α-amination of an aldehyde with an azodicarboxylate as the electrophile using L -proline enamine catalysis in 2002. Following borohydride reduction, the α-hydrazino alcohol was obtained in high yield (93-99%) and enantioselectivity (86-97%). Application of the enantioselective α-amination reaction to an acetal as a masked aldehyde was developed in our group recently, and in part I of this thesis results on extending this chemistry to the α-amination of N-protected hemiaminals from N-heterocycles are reported, in which it was found that the reaction only worked with the carbonyl group exo to the ring. In the case of the hemiaminal derived from N-Boc or N-CBz 2-pyrrolidinone an amination with proline catalyst in acetonitrile over 3 days gave α-aminated products in high ee (77-84%). N-N bond hydrogenolysis using Raney Nickel and hydrogen, followed by oxidation to the lactam afforded the N -protected α-amino lactam in high enantioselectivity (78% and 8 6 %). In part II the development of a mild reduction of the N-N bond of the α-hydrazino amination products of straight-chain aldehydes is reported. The corresponding oxazolidinone- hydrazides are reduced to their oxazolidinones via a modified E1cB elimination using ethyl bromomalonate and potassium carbonate in acetonitrile. The reactions gave high yields (76-96%) and ees (83-95%) with a good chemoselectivity profile.","abstract_has_math":false,"creators":["Ramaotsoa, Valerie"],"institution":"Department of Chemistry","degree_name":null,"degree_level":null,"degree_discipline":null,"degree_department":null,"school":null,"contributors":[],"advisors":["Hunter, Roger"],"committee_chairs":[],"committee_members":[],"year":2015,"date_issued":"2015","date_published":"2015","updated_at":"2026-07-22T22:23:42Z","subjects":[],"languages":["eng"],"rights":[],"rights_urls":[],"identifier_entries":[]},"links":{"outbound_url":"http://hdl.handle.net/11427/15706","outbound_label":"Handle","outbound_source":"dc:identifier.uri"},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:contributor.advisor","label":"Advisor","values":["Hunter, Roger"]},{"key":"dc:creator","label":"Author","values":["Ramaotsoa, Valerie"]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date.accessioned","label":"Dc Date Accessioned","values":["2015-12-08T11:49:39Z"]},{"key":"dc:date.available","label":"Dc Date Available","values":["2015-12-08T11:49:39Z"]},{"key":"dc:date.issued","label":"Date","values":["2015"]},{"key":"dc:publisher.department","label":"Dc Publisher Department","values":["Department of Chemistry"]},{"key":"dc:publisher.institution","label":"Dc Publisher Institution","values":["University of Cape Town"]},{"key":"dc:type","label":"Dc Type","values":["Master Thesis"]},{"key":"dc:type.qualificationlevel","label":"Dc Type Qualificationlevel","values":["Masters"]},{"key":"dc:type.qualificationname","label":"Dc Type Qualificationname","values":["MSc"]}]},{"id":"language_rights","label":"Language and Rights","entries":[{"key":"dc:language.iso","label":"Language (ISO)","values":["eng"]}]},{"id":"identifiers","label":"Identifiers","entries":[{"key":"dc:identifier.uri","label":"Identifier URI","values":["http://hdl.handle.net/11427/15706"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description.abstract","label":"Abstract","values":["Jorgensen and List introduced enantioselective α-amination of an aldehyde with an azodicarboxylate as the electrophile using L -proline enamine catalysis in 2002. Following borohydride reduction, the α-hydrazino alcohol was obtained in high yield (93-99%) and enantioselectivity (86-97%). Application of the enantioselective α-amination reaction to an acetal as a masked aldehyde was developed in our group recently, and in part I of this thesis results on extending this chemistry to the α-amination of N-protected hemiaminals from N-heterocycles are reported, in which it was found that the reaction only worked with the carbonyl group exo to the ring. In the case of the hemiaminal derived from N-Boc or N-CBz 2-pyrrolidinone an amination with proline catalyst in acetonitrile over 3 days gave α-aminated products in high ee (77-84%). N-N bond hydrogenolysis using Raney Nickel and hydrogen, followed by oxidation to the lactam afforded the N -protected α-amino lactam in high enantioselectivity (78% and 8 6 %). In part II the development of a mild reduction of the N-N bond of the α-hydrazino amination products of straight-chain aldehydes is reported. The corresponding oxazolidinone- hydrazides are reduced to their oxazolidinones via a modified E1cB elimination using ethyl bromomalonate and potassium carbonate in acetonitrile. The reactions gave high yields (76-96%) and ees (83-95%) with a good chemoselectivity profile."]},{"key":"dc:title","label":"Title","values":["Hemiaminals : a new chemotype for organocatalysis"]}]}],"canonical_facts":{"dc:contributor.advisor":["Hunter, Roger"],"dc:creator":["Ramaotsoa, Valerie"],"dc:date.accessioned":["2015-12-08T11:49:39Z"],"dc:date.available":["2015-12-08T11:49:39Z"],"dc:date.issued":["2015"],"dc:description.abstract":["Jorgensen and List introduced enantioselective α-amination of an aldehyde with an azodicarboxylate as the electrophile using L -proline enamine catalysis in 2002. Following borohydride reduction, the α-hydrazino alcohol was obtained in high yield (93-99%) and enantioselectivity (86-97%). Application of the enantioselective α-amination reaction to an acetal as a masked aldehyde was developed in our group recently, and in part I of this thesis results on extending this chemistry to the α-amination of N-protected hemiaminals from N-heterocycles are reported, in which it was found that the reaction only worked with the carbonyl group exo to the ring. In the case of the hemiaminal derived from N-Boc or N-CBz 2-pyrrolidinone an amination with proline catalyst in acetonitrile over 3 days gave α-aminated products in high ee (77-84%). N-N bond hydrogenolysis using Raney Nickel and hydrogen, followed by oxidation to the lactam afforded the N -protected α-amino lactam in high enantioselectivity (78% and 8 6 %). In part II the development of a mild reduction of the N-N bond of the α-hydrazino amination products of straight-chain aldehydes is reported. The corresponding oxazolidinone- hydrazides are reduced to their oxazolidinones via a modified E1cB elimination using ethyl bromomalonate and potassium carbonate in acetonitrile. The reactions gave high yields (76-96%) and ees (83-95%) with a good chemoselectivity profile."],"dc:identifier.uri":["http://hdl.handle.net/11427/15706"],"dc:language.iso":["eng"],"dc:publisher.department":["Department of Chemistry"],"dc:publisher.institution":["University of Cape Town"],"dc:title":["Hemiaminals : a new chemotype for organocatalysis"],"dc:type":["Master Thesis"],"dc:type.qualificationlevel":["Masters"],"dc:type.qualificationname":["MSc"]},"updated_at":"2026-07-22T22:23:42Z"}